Dihalocyclopropyl aromatic carboxylic acid



United States Patent Ofi ice 3,373,396 Patented Mar. 12, 1968 3,373,190 DIHALOCYCLOPROPYL AROMATIC CARBOXYLIC ACID Ivan C. Popoif, Ambler, and Bernard Loev, Broomall, Pa.,

assignors to Pennsalt Chemicals Corporation, Philadelphia, Pa., a corporation of Pennsylvania No Drawing. Continuation-impart of application Ser. N 0. 724,527, Mar. 28, 1958. This application Apr. 26, 1965, Ser. No. 451,032

4 Claims. (Cl. 260-515) /O l l such as 1,2-dimethyl-3,S-dichlorocyclopropane or 1,Z-dimethyl-3,3-dibromocyclopropane Br Br CH;C -COH H H are known. Compounds of this type are characterized by unusual chemical inertness. Since they are saturated compounds, however, and contain no reactive substituents they have limited utility since it is difficult to convert them to desired derivatives.

A new series of compounds of excellent utility have now been found which contain the dichlorocyclopropyl group Cl Cl l I together with a neighboring carbon to carbon double bond. Specifically the new compounds are aromatic carboxylic acids characterized by the presence of a -C CC= l l l I group wherein the I group is part of an aromatic ring. The carbons of the dichlorocyclopropyl group.

are other than those in an aromatic ring. The term aromatic ring as used herein includes carbocyclic rings of the benzene series, including for example benzene, naphthalene, anthracene, etc.

The class of dichlorocyclopropyl compounds within the scope of the invention are those in which the double bond neighboring to the dichlorocyclopropane group is a double bond in a carbocyclic aromatic ring (that is, part of a carbocyclic aromatic ring) such as in the following compounds:

(particularly when the vinyl group is ortho or para to the dichlorocyclopropyl group).

Cl\ /Cl H2C-CH C O O H The new compounds of the invention may be prepared by reacting chloroform, CHCI with compounds in which an olefinic double bond is conjugated with an aromatic double bond such as vinyl substituted aromatic compounds which have a ring substituted functional group capable of being converted to the acid. Thus, divinylbenzene, di-vinylnaphthalene, and the like with 1 mole of chloroform and subsequently oxidized to form the acid from the remaining vinyl substituent.

1 COOH The reaction with CHCl should be carried out in the presence of an alkali metal alkoxide such as potassium tertiary butoxide, sodium methoxide, or potassium tertiary-amylate. The preferred alkali metal alkoxide is potassium tertiary butoxide. For best results the reaction should be carried out under anhydrous conditions.

The solvent for the reaction may be an alcohol, and preferably an alcohol corresponding to the alkali metal alkoxide, particularly tertiary butyl alcohol. Under some circumstances, other inert solvents may be employed '3 such as benzene, diethylether, dioxane, petroleum ether and the like. 7

The reaction is generally carried out over the temperature range of from 50 C. to +100 C. although lower temperatures can be use-d where required in the handling of low boiling compounds. The preferred temperature range is -20 C. to +40 C. The reaction may be carried out at sub-atmospheric, atmospheric or superatmospheric pressures, although in most instances the reaction is readily carried out at atmospheric pressures, and atmospheric pressures are accordingly preferred.

Example 1 In a four necked flask equipped with a stirrer, thermometer well, dropping funnel, and Dry Ice condenser with a CaCl drying tube, there is placed a solution of 650 grams (5 moles) of commercial grade divinylbenzene in 240 grams (2 moles) of CHCl The divinylbenzene is a mixture having a narrow boiling range and containing the various divinylbenzene isomers (predominately ortho and meta with some para) as well as some ethyl vinylbenzene. The flask and contents are chilled and 250 grams (2 moles) of a suspension of potassium tertiary amylate in hexane is gradually added to the chilled solution. The reaction temperature is maintained at 15 C. by means of a cooling bath. After the addition is complete, the reaction is stirred another hour at 15 C. and overnight at 25 C. The salt (KCl) is filtered off, and the solution is then washed with water, dried and distilled in vacuo.

After removal of the unreacted divinylbenzene and ethyl vinylbenzene, a fraction is obtained consisting of the various isomers (predominately ortho and para) of (2,2-dichlorocyclopropyl) -vinylbenzene H2O CE.

CH=CH2 The oxidation to the acid may be readily carried out by use of standard oxidizing agents, such as potassium permanganate or potassium dichrornate. A particularly advantageous method of oxidation involves the use of ozone to form an ozonide at the double bond. The ozonide, on treatment with hydrogen peroxide, gives the corresponding acid.

A solution of 15 grams of the (2,2-dichlorocyclopropyl) vinylbenzene is ethyl acetate is ozonized by passing a stream of ozone into the solution at a temperature of about 0 C. Care is taken not to use excess ozone to avoid attack of the aromatic ring. The ozonide solution is the refluxed with 35% hydrogen peroxide, and the solvent and water are removed by vacuum distillation, leaving a waxy solid, (2,2-dichlorocyclopropyl).benzoic The compounds of the invention have utility as herbicides, insecticides, particularly as fumigants; bactericides, lubricants, plasticizers, lube oil additives and pharma ceuticals.

l/Ve claim:

1. A 1-(2,2-dihalocyclopropyl) aromatic carboxylic acid having the formula wherein Ar is an aromatic hydrocarbon group, n is 1, m is 1, and wherein R is hydrogen and X is chlorine.

2. A benzoic acid having the formula wherein R is hydrogen and X is chlorine.

3. p-(2,Z-dichlorocyclopropyl) benzoic acid. 4. o-(2,2-dichlorocycloproyl) benzoic acid.

References Cited UNITED STATES PATENTS 3,157,697 11/1964 Sandri et al. 260-515 LORRAINE A. WEINBERC'ER, Primary Examiner.

T. L. GALLOWAY, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,373,190 March 12, 1968 Ivan C. Popoff et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, lines 45 to 53, the lefthand portion of the equation should appear as shown below instead of as in the patent:

CH=CH CH=CH2 column 4, line 2, for "is", first occurrence, read in line 6, for "the", flISt occurrence, read then line 38, for "o-(2,2dich1orocyc1oproy1" read o-2,2-dichlorocyclopropyl Signed and sealed this 1st day of July 1969.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Patents 

1. A 1-(2,2-DIHALOCYCLOPROPYL) AROMATIC CARBOXYLIC ACID HAVING THE FORMULA 